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Dyes and Pigments 49 (2001) 117125
www.elsevier.com/locate/dyepig
Received 24 October 2000; received in revised form 4 December 2000; accepted 15 March 2001
Abstract
The photocatalytic degradation of various dyes (Orange II, Orange G, Congo Red, Indigo Carmine, Crystal Violet,
Malachite Green, Remazol Blue and Methyl Yellow) has been studied, using P25 Degussa as catalyst. All dye solutions
underwent a decolourization. The kinetics of reaction have been studied and were found to be zero or rst order with
respect to the dyes. This was compared with the adsorption properties. The eect of the addition of hydrogen peroxide
has been studied. An enhancement of the rate has been observed in all cases and the order with respect to the additive
was found to be almost zero. It is dicult to give a general picture of the kinetics using these very dierent dyes but the
process was found to be eective for the decolourization of textile wastewater. # 2001 Published by Elsevier Science
Ltd.
Keywords: Dyes; Decolourization; Photocatalysis; Kinetics; Hydrogen peroxide; Textile industry
generated when the photocatalyst is illuminated in Fluka. Puried water was obtained from an Elix
the presence of water and air [1214], these ultra Millipore equipment. The titanium dioxide used,
reactive species associated with oxygen are able to TITANDIOXID P25 Degussa, was about 70%
achieve a complete mineralization of organic pol- anatase. According to the manufacturers speci-
lutants into carbon dioxide, water and other non- cations [17], the elementary particle in dry powder
toxic products [15,16]. was approximately spherical in shape with a size
The aim of this study is to analyse the kinetics of of 20 nm. The specic surface area, as measured
decolourization of various types of dyes and to by N2 adsorption at 77 K, was 44 m2 g1 [18].
assess the inuence additives have on the process. The experimental set-up for the photocatalytic
decolourization has been described previously [19].
The photocatalyst has been deposited on 3.848
2. Experimental procedures cm2 glass plates from a suspension of TiO2.
The dyes Orange II, Orange G, Congo Red, A suspension of commercial Degussa P25 TiO2
Indigo Carmine, Crystal Violet, Malachite Green, of 4 g l1 in pure water was prepared, the pH was
Remazol Blue and Methyl Yellow were commercial adjusted to about 3 and it was sonicated. A given
products purchased from Sigma Chemical Co., and volume suspension was carefully poured on the
used without further purication (see Fig. 1). glass plate and allowed to dry out at 100 C for a
Hydrogen peroxide (30%, w/w) was obtained from few hours.
After drying, the plate was red at 475 C for 4 h solution was 0.2 l. The solution was continuously
(Fig. 2). During the heating, OH groups from the circulated with a peristaltic pump, owing freely
catalyst surface and the support can react and lose a over the catalytic surface and stirred in the 0.1 l
molecule of water, creating an oxygen bridge, thus tank and could be considered as being constantly
increasing the adherence of the catalyst to the air-equilibrated. The circulating ow was 0.4 l
support. Before deposition, the glass surface was min1.
treated using a dilute acid solution of HF and As the extent of adsorption or photocatalytic
washed in a basic solution of NaOH in order to degradation was very small during a single pass
increase the number of OH groups. The suspension (0.5 min), the whole system could be considered as
concentration 4 g l1 was chosen so as to get thin a perfectly stirred sealed reactor with respect to
enough deposits. This deposition process was car- the solution. Irradiation of the photocatalyst was
ried out four times in succession so as to increase carried out by a MAZDA-TFN18 18 W UV
the total thickness. As shown in Fig. 3, the rst uorescent lamp emitting around 365 nm and
coat does not cover all the surface but additional positioned parallel to the plate. The average ux
coats lead to a complete coverage. on the plate was estimated to be about 2.103 E
After each run, the catalyst was washed and min1 m2 [20]. Adsorption measurements were
irradiated for several hours in the presence of H2O2 made using the same set-up in the absence of
so that it was regenerated. irradiation.
Electron microscopy was carried out on a Jeol Absorption measurements to monitor the dye
T33OA scanning microscope with the help of the concentration in the aqueous phase were carried
LSGC Laboratory. Prolometry measurements out on a Lambda-2 Perkin-Elmer UV/vis spectro-
were carried out on a UBM optical prolometer photometer.
equipped with a MICROFOCUS probe. Fig. 4
shows the topology of a TiO2 deposit which shows
a uniform surface of roughness of about 5 mm. In 3. Results and discussion
addition, the average thickness was estimated to
be 10 mm [20]. BET areas were determined on a The kinetics of photocatalytic degradation of the
FISON Sorptomatic 1900 sorptometer. various dyes are pictured in Fig. 6ag, as the
Photocatalytic measurements were carried out decrease in the relative concentration C/C of the
on a homemade reactor designed for testing 3.8 dye with the time of irradiation, where C is the run-
48 cm2 at glass plates carrying the deposited lm ning concentration and C the concentration at the
of catalyst (Fig. 5). The total volume of aqueous beginning of the irradiation. Note that the solution
Fig. 6. (a) Photocatalytic degradation of Orange II following dark adsorption (&C =9.9 105 mol l1, irradiation ux 7 107 E
min1); eect of H2O2 (&103 mol l1, * 102 mol l1, * 2 102 mol l1, ~ 5 102 mol l1, ~ 101 mol l1). (b) Photocatalytic
degradation of Orange G (C =9.9 105 mol l1), same conditions as in Fig. 6a. (c) Photocatalytic degradation of Congo Red (C =3.5
105 mol l1), same conditions as in Fig. 6a. (d) Photocatalytic degradation of Indigo Carmine (C =9.5 105 mol l1), same condi-
tions as in Fig. 6a. (e) Photocatalytic degradation of Crystal Violet (C =1.8 105 mol l1), same conditions as in Fig. 6a. (f) Photo-
catalytic degradation of Malachite Green (C =1.9 105 mol l1), same conditions as in Fig. 6a. (g) Photocatalytic degradation of
Remazol Blue (C =9.6 105 mol l1), same conditions as in Fig. 6a.
C. Hachem et al. / Dyes and Pigments 49 (2001) 117125 123
Table 1
Properties and kinetics parameters of various dyes
Fig. 8. Equilibrium between the two tautomeric forms in the acid dye Orange II.